The present invention relates to a novel fluorine compound and surfactant that can impart surface functions such as water and oil repelling properties, antifouling property and antistatic property as well as an aqueous coating composition and silver halide photographic light-sensitive material utilizing them.
Compounds having a fluorinated alkyl chain are conventionally known as surfactants. Such surfactants enables modifications of various surface properties by the unique properties of the fluorinated alkyl chain (e.g., water and oil repelling properties, lubricity, antistatic property etc.), and they are used for surface treatment of base materials of a wide range such as fibers, cloth, carpets and resins. Further, if a surfactant having a fluorinated alkyl chain (henceforth referred to as a xe2x80x9cfluorine-containing surfactantxe2x80x9d) is added to a solution of any of various substrates in an aqueous medium, not only a uniform coating film can be formed without repellency upon coating, but also a surfactant-adsorbed layer can be formed on a substrate surface and thus the unique properties provided by the fluorinated alkyl chain can be imparted to the surface of coating.
Also in photographic light-sensitive materials, various surfactants are used and play important roles. Photographic light-sensitive materials are usually produced by separately coating a plurality of coating solutions including an aqueous solution of a hydrophilic colloid binder (e.g., gelatin) on a support to form multiple layers. Multiple hydrophilic colloid layers are often simultaneously coated as stacked layers. These layers include antistatic layer, undercoat layer, antihalation layer, silver halide emulsion layer, intermediate layer, filter layer, protective layer and so forth, and various materials for exerting functions of the layers are added to the layers. Further, polymer latex may also be added to the hydrophilic colloid layer in some cases in order to improve physical properties of film. Furthermore, in order to add functional compounds hardly soluble in water such as color couplers, ultraviolet absorbers, fluorescent brightening agents and lubricants to the hydrophilic colloid layer, these materials are sometimes emulsion-dispersed in a hydrophilic colloid solution as they are or as a solution in a high boiling point organic solvent such as phosphoric acid ester compounds and phthalic acid ester compounds for the preparation of a coating solution. As described above, photographic light-sensitive materials are generally constituted by various hydrophilic colloid layers, and in the production of them, it is required to uniformly coat coating solutions containing various materials at a high speed without defects such as repelling and uneven coating. In order to meet such requirements, a surfactant is often added to a coating solution as a coating aid.
Meanwhile, photographic light-sensitive materials are brought into contact with various materials during production, light exposure and development thereof. For example, if a light-sensitive material is in a rolled shape in process steps, a back layer formed on the back surface of the support may contact with the surface layer. Further, when it is transported during process steps, it may contact with stainless steel rollers, rubber rollers etc. When they are brought into contact with these materials, surfaces (gelatin layer) of light-sensitive materials are likely to be positively charged and they may undesirably cause discharge as the case may be. Therefore, there may remain undesirable traces of light exposure (called static marks) on the light-sensitive materials. In order to reduce this electrification property of gelatin, a compound containing a fluorine atom is effective, and a fluorine-containing surfactant is often added.
As described above, surfactants, especially fluorine-containing surfactants, are used as materials having both of the function as coating aids for providing uniformity of coated films and the function for imparting antistatic property to photographic light-sensitive materials. Specific examples thereof are disclosed in, for example, Japanese Patent Laid-open Publication (Kokai, henceforth referred to as JP-A) No. 49-46733, JP-A-51-32322, JP-A-57-64228, JP-A-64-536, JP-A-2-141739, JP-A-3-95550, JP-A-4-248543 and so forth. However, these materials do not necessarily have performance satisfying the demands for higher sensitivity and coating at higher speed required for recent photographic light-sensitive materials, and it is desired to further improve fluorine-containing surfactants. Although it is generally considered that a shorter perfluoroalkyl chain would be advantageous in degradability (degradability of compound after use), it markedly degrades orientation of the fluorinated alkyl chain on the surface of coated film. Therefore, it is strongly desired to develop a fluorine-containing surfactant that has a shorter fluoroalkyl chain and can also provide both of surface orientation (it relates to antistatic property) and uniformity of coated film.
An object of the present invention is to provide a novel fluorine compound that has a short perfluoroalkyl group, but shows superior surface orientation and enables formation of uniform coated films when used in formation of coated films, and a surfactant containing it. Another object of the present invention is to provide an aqueous coating composition that enables formation of uniform coated films having antistatic property. A further object of the present invention is to provide a silver halide photographic light-sensitive material that can be stably produced and is imparted with antistatic property.
In order to achieve the aforementioned objects, the silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having one or more layers including a light-sensitive silver halide emulsion layer on a support, wherein any of the layers contains a compound represented by the following formula (1). 
In the formula, R1 and R2 each represent a substituted or unsubstituted alkyl group provided that at least one of R1 and R2 represents an alkyl group substituted with one or more fluorine atoms. R3, R4 and R5 each independently represent a hydrogen atom or a substituent, X1, X2 and Z each independently represent a divalent bridging group or a single bond, and M+ represents a cationic substituent. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1.
As preferred embodiments of the present invention, there are provided the aforementioned silver halide photographic light-sensitive material, which has a light-insensitive hydrophilic colloid layer as an outermost layer and contains a compound represented by the aforementioned formula (1) in the outermost layer; and the aforementioned silver halide photographic light-sensitive material, which contains a compound represented by the aforementioned formula (1) and an anionic or nonionic surfactant in the outermost layer. As a preferred embodiment of the present invention, there is also provided the aforementioned silver halide photographic light-sensitive material, wherein the compound represented by the aforementioned formula (1) is a compound represented by the following general following formula (1-a), and as a more preferred embodiment of the present invention, there is provided the aforementioned silver halide photographic light-sensitive material, wherein the compound represented by the aforementioned formula (1) is a compound represented by the following general following formula (1-c). 
In the formula, R11 and R21 each represent a substituted or unsubstituted alkyl group provided that at least one of R11 and R21 represents an alkyl group substituted with one or more fluorine atoms and the total carbon atom number of R11 and R21 is 19 or less. R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group and two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. X11 and X21 each independently represent xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94 where R31 represents a hydrogen atom or a substituent, and Z represents a divalent bridging group or a single bond. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1. 
In the formula, n1 represents an integer of 1-6 and n2 represents an integer of 3-8 provided that 2(n1+n2) is 19 or less. R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group and two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. X11 and X21 each independently represent xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94 where R31 represents a hydrogen atom or a substituent, and Z represents a divalent bridging group or a single bond. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1.
Further, as a preferred embodiment of the present invention, there is provided the aforementioned silver halide light-sensitive material, wherein the silver halide emulsion layer contains an emulsion in which 50% or more of total projected area of silver halide grains is provided by tabular grains having an aspect ratio of 3 or more.
In order to achieve the aforementioned objects, the present invention provides a fluorine compound represented by the aforementioned formula (1-a), a surfactant containing a compound represented by the aforementioned formula (1-a), and an aqueous coating composition containing a compound represented by the aforementioned formula (1-a).
Hereafter, the present invention will be explained in detail. In the present specification, ranges indicated with xe2x80x9cxe2x88x92xe2x80x9d mean ranges including the numerical values before and after xe2x80x9cxe2x88x92xe2x80x9d as the minimum and maximum values.
[Fluorine Compound and Surfactant]
First, the fluorine compound and surfactant of the present invention will be explained. The fluorine compound of the present invention is represented by the aforementioned formula (1). The fluorine compound of the present invention can be used as a surfactant.
In the formula (1), R1 and R2each represent a substituted or unsubstituted alkyl group provided that at least one of R1 and R2 represents an alkyl group substituted with one or more fluorine atoms. R3, R4 and R5 each independently represent a hydrogen atom or a substituent, X1, X2 and Z each independently represent a divalent bridging group or a single bond, and M+ represents a cationic substituent. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1.
In the aforementioned formula (1), R1 and R2 each represent a substituted or unsubstituted alkyl group. The alkyl group contains one or more carbon atoms and may be a straight, branched or cyclic alkyl group. Examples of the substituent include a halogen atom, an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carbonamido group, a carbamoyl group, an oxycarbonyl group, a phosphoric acid ester group and so forth. However, at least one of R1 and R2 represents an alkyl group substituted with one or more fluorine atoms (an alkyl group substituted with one or more fluorine atoms is referred to as xe2x80x9cRfxe2x80x9d hereafter).
Rf is an alkyl group having one or more carbon atoms and substituted with at least one fluorine atom. It is sufficient that Rf should be substituted with at least one fluorine atom, and it may have any of straight, branched and cyclic structures. It may be further substituted with a substituent other than fluorine atom or substituted with only fluorine atom or atoms. Examples of the substituent of Rf other than fluorine atom include an alkenyl group, an aryl group, an alkoxyl group, a halogen atom other than fluorine, a carboxylic acid ester group, a carboneamido group, a carbamoyl group, an oxycarbonyl group, a phosphoric acid ester group and so forth.
Rf may be a fluorine-substituted alkyl group having preferably 1-16 carbon atoms, more preferably 1-12 carbon atoms, further preferably 4-10 carbon atoms. Preferred examples of Rf include xe2x80x94(CH2)2xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)3xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)2xe2x80x94(CF2)6xe2x80x94F, xe2x80x94(CH2)6xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)2xe2x80x94(CF2)8xe2x80x94F, xe2x80x94CH(CF3)2, xe2x80x94(CH2)xe2x80x94(CF2)4xe2x80x94H, xe2x80x94(CH2)xe2x80x94(CF2)6xe2x80x94H, xe2x80x94(CH2)2xe2x80x94(CF2)8xe2x80x94H and so forth.
Rf is more preferably an alkyl group having 4-10 carbon atoms and substituted with a trifluoromethyl group at its end, particularly preferably an alkyl group having 3-10 carbon atoms represented as xe2x80x94(CH2)n1xe2x80x94(CF2)n2xe2x80x94F (n1 represents an integer of 1-6, and n2 represents an integer of 3-8). Specific examples thereof include xe2x80x94CH2xe2x80x94(CF2)2xe2x80x94F, xe2x80x94(CH2)6xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)3xe2x80x94(CF2)4xe2x80x94F, xe2x80x94CH2xe2x80x94(CF2)3xe2x80x94F, xe2x80x94(CH2)2xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)3xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)6xe2x80x94(CF2)4xe2x80x94F, xe2x80x94(CH2)2xe2x80x94(CF2)6xe2x80x94F, xe2x80x94(CH2)3xe2x80x94(CF2)6xe2x80x94F, xe2x80x94(CH2)2xe2x80x94(CF2)6xe2x80x94F and so forth. Among these, xe2x80x94(CH2)2xe2x80x94(CF2)4xe2x80x94F and xe2x80x94(CH2)2xe2x80x94(CF2)6xe2x80x94F are particularly preferred.
In the aforementioned formula (1), both of R1 and R2 preferably represent Rf.
When R1 and R2 represent an alkyl group other than Rf, i.e., an alkyl group that is not substituted with a fluorine atom, the alkyl group preferably represents a substituted or unsubstituted alkyl group having 1-24 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 6-24 carbon atoms. Preferred examples of the unsubstituted alkyl group having 6-24 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl, docosyl group, tetracosyl group, 2-decyltetradecyl group, tricosyl group, cyclohexyl group, cycloheptyl group and so forth. Further, preferred examples of the substituted alkyl group having a total carbon number of 6-24 include 2-hexenyl group, oleyl group, linoleyl group, linolenyl group, benzyl group, xcex2-phenethyl group, 2-methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, 12-(p-chlorophenyl)dodecyl group, 2-(diphenyl phosphate)ethyl group and so forth.
The alkyl group other than Rf represented by R1 or R2 is more preferably a substituted or unsubstituted alkyl group having 6-18 carbon atoms. Preferred examples of the unsubstituted alkyl group having a carbon number of 6-18 include n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, 4-tert-butylcyclohexyl group and so forth. Further, preferred examples of the substituted alkyl group having a total carbon number of 6-18 include phenethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl, oleyl group, linoleyl group, linolenyl group and so forth.
The alkyl group other than Rf represented by R1 or R2 is particularly preferably n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, oleyl group, linoleyl group or linolenyl group, most preferably a straight, cyclic or branched unsubstituted alkyl group having a carbon number of 8-16.
In the aforementioned formula (1), R3, R4 and R5 each independently represent a hydrogen atom or a substituent. Examples of the substituent include, for example, an alkyl group having preferably 1-20 carbon atoms, more preferably 1-12 carbon atoms, particularly preferably 1-8 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group etc.), an alkenyl group having preferably 2-20 carbon atoms, more preferably 2-12 carbon atoms, particularly preferably 2-8 carbon atoms (e.g., vinyl group, allyl group, 2-butenyl group, 3-pentenyl group etc.), an alkynyl group having preferably 2-20 carbon atoms, more preferably 2-12 carbon atoms, particularly preferably 2-8 carbon atoms (e.g., propargyl group, 3-pentynyl group etc.), an aryl group having preferably 6-30 carbon atoms, more preferably 6-20 carbon atoms, particularly preferably 6-12 carbon atoms (e.g., phenyl group, p-methylphenyl group, naphthyl group etc.), a substituted or unsubstituted amino group having preferably 0-20 carbon atoms, more preferably 0-10 carbon atoms, particularly preferably 0-6 carbon atoms (e.g., unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, dibenzylamino group etc.), an alkoxy group having preferably 1-20 carbon atoms, more preferably 1-12 carbon atoms, particularly preferably 1-8 carbon atoms (e.g., methoxy, ethoxy, butoxy etc.), an aryloxy group having preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms (e.g., phenyloxy group, 2-naphthyloxy group etc.), an acyl group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., acetyl group, benzoyl group, formyl group, pivaloyl group etc.), an alkoxycarbonyl group having preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group etc.), an aryloxycarbonyl group having preferably 7-20 carbon atoms, more preferably 7-16 carbon atoms, particularly preferably 7-10 carbon atoms (e.g., phenyloxycarbonyl group etc.), an acyloxy group having preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms (e.g., acetoxy group, benzoyloxy group etc.), an acylamino group having preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms (e.g. acetylamino group, benzoylamino group etc.), an alkoxycarbonylamino group having preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms (e.g., methoxycarbonylamino group etc.), an aryloxycarbonylamino group having preferably 7-20 carbon atoms, more preferably 7-16 carbon atoms, particularly preferably 7-12 carbon atoms (e.g., phenyloxycarbonylamino group etc.), a sulfonylamino group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., methanesulfonylamino group, benzenesulfonylamino group etc.), a sulfamoyl group having preferably 0-20 carbon atoms, more preferably 0-16 carbon atoms, particularly preferably 0-12 carbon atoms (e.g., sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group etc.), a carbamoyl group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, phenylcarbamoyl group etc.), an alkylthio group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., methylthio group, ethylthio group etc.), an arylthio group having preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, particularly preferably 6-12 carbon atoms (e.g., phenylthio group etc.), a sulfonyl group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., mesyl group, tosyl group etc.), a sulfinyl group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., methanesulfinyl group, benzenesulfinyl group etc.), a ureido group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., unsubstituted ureido group, methylureido group, phenylureido group etc.), a phosphoric acid amido group having preferably 1-20 carbon atoms, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms (e.g., diethylphosphoric acid amido group, phenylphosphoric acid amido group etc.), a hydroxyl group, a mercapto group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group having preferably 1-30 carbon atoms, more preferably 1-12, for example, such a heterocyclic group containing a hetero atom of nitrogen atom, oxygen atom, sulfur atom or the like (e.g., imidazolyl group, pyridyl group, quinolyl group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group etc.), a silyl group having preferably 3-40 carbon atoms, more preferably 3-30 carbon atoms, particularly preferably 3-24 carbon atoms (e.g., trimethylsilyl group, triphenylsilyl group, etc.) and so forth. These substituents may be further substituted with other substituents. Further, two or more substituents exist, they may be identical to or different from each other or one another. If possible, they may bond to each other to form a ring.
R3, R4 and R5 preferably represent an alkyl group or a hydrogen atom, more preferably a hydrogen atom.
In the aforementioned formula, X1 and X2 each represent a divalent bridging group or a single bond. Although the aforementioned divalent bridging group is not particularly limited, it is preferably an arylene group, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94NR31xe2x80x94 (R31 represents a hydrogen atom or a substituent, the substituent may be any of the groups exemplified as substituents represented by R3, R4 and R5, and R31 is preferably an alkyl group, the aforementioned Rf or a hydrogen atom, more preferably a hydrogen atom) or a group consisting a combination of these groups, more preferably xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94. X1 and X2 more preferably represent xe2x80x94Oxe2x80x94 or xe2x80x94NR31xe2x80x94, further preferably xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94, particularly preferably xe2x80x94Oxe2x80x94.
In the aforementioned formula, Z represents a divalent bridging group or a single bond. Although the divalent bridging group is not particularly limited, it is preferably an alkylene group, an arylene group, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94S(xe2x95x90O)xe2x80x94, xe2x80x94S(xe2x95x90O)2xe2x80x94, xe2x80x94NR32xe2x80x94 (R32 represents a hydrogen atom or a substituent, the substituent may be any of the groups exemplified as substituents represented by R3, R4 and R5, and R32 is preferably an alkyl group or a hydrogen atom, more preferably a hydrogen atom) or a group consisting a combination of these groups, more preferably an alkylene group having 1-12 carbon atoms, an arylene group 6-12 carbon atoms, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94S(xe2x95x90O)xe2x80x94, xe2x80x94S(xe2x95x90O)2xe2x80x94, xe2x80x94NR32xe2x80x94 or a group consisting a combination of the foregoing groups. Z is more preferably an alkylene group having 1-8 carbon atoms, xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94S(xe2x95x90O)xe2x80x94, xe2x80x94S(xe2x95x90O)2xe2x80x94, xe2x80x94NR32xe2x80x94 or a group consisting a combination of these groups, and examples thereof are xe2x80x94(CH2)2xe2x80x94Sxe2x80x94, xe2x80x94(CH2)2xe2x80x94NHxe2x80x94, xe2x80x94(CH2)3xe2x80x94NHxe2x80x94, xe2x80x94(CH2)2xe2x80x94COxe2x80x94NHxe2x80x94, xe2x80x94(CH2)2xe2x80x94Sxe2x80x94CH2xe2x80x94, xe2x80x94(CH2)2xe2x80x94NHxe2x80x94CH2xe2x80x94, xe2x80x94(CH2)3xe2x80x94NHxe2x80x94CH2xe2x80x94 and so forth.
In the aforementioned formula, M+ represents a cationic substituent, preferably an organic cationic substituent, more preferably an organic cationic substituent containing a nitrogen or phosphorus atom. It is further preferably a pyridinium cation or ammonium cation group, and it is particularly preferably a trialkylammonium cation group represented by the following formula (2). 
In the above formula, R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group. As the substituent, those exemplified above as the substituents represented by R3, R4 and R5 can be used. Further, if possible, two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. R13, R14 and R15 preferably represent an alkyl group having 1-12 carbon atoms, more preferably an alkyl group having 1-6 carbon atoms, further preferably methyl group, ethyl group or methylcarboxyl group, particularly preferably methyl group.
In the aforementioned formula, Yxe2x88x92 represents a counter anion, and it may be an inorganic anion or an organic anion. When the charge excluding Yxe2x88x92 is 0, there may not be Yxe2x88x92. The inorganic anion is preferably iodide ion, bromide ion, chloride ion or the like, and the organic ion is preferably p-toluenesulfonate ion, benzenesulfonate ion, methanesulfonate ion, trifluoromethanesulfonate ion or the like. Yxe2x88x92 is more preferably iodide ion, p-toluenesulfonate ion, or benzenesulfonate ion, particularly preferably p-toluenesulfonate ion.
In the aforementioned formula, m represents 0 or 1, preferably 0.
Among the compounds represented by the aforementioned formula (1), the compounds represented by the aforementioned formula (1-a) are preferred.
In the formula (1-a), R11 and R21 each represent a substituted or unsubstituted alkyl group provided that at least one of R11 and R21 represents an alkyl group substituted with one or more fluorine atoms and the total carbon atom number of R11 and R21 is 19 or less. R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group and two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. X11 and X21 each independently represent xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94 where R31 represents a hydrogen atom or a substituent, and Z represents a divalent bridging group or a single bond. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1. In the formula, Z and Yxe2x88x92 have the same meanings as defined in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1). R13, R14, R15 and m have the same meanings as defined in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1).
In the formula, X11 and X21 each represent xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94 (R31 represents a hydrogen atom or a substituent, the substituent may be any of the groups exemplified as substituents represented by R3, R4 and R5, and R31 is preferably an alkyl group, the aforementioned Rf or a hydrogen atom, more preferably a hydrogen atom), more preferably xe2x80x94Oxe2x80x94 or xe2x80x94NHxe2x80x94, further preferably xe2x80x94Oxe2x80x94.
In the aforementioned formula, R11 and R21 have the same meanings as R1 and R2 in the formula (1), respectively, and the preferred scopes thereof are also the same as those of R1 and R2. However, the total carbon atom number of R11 and R21 is 19 or less. m is 0 or 1.
Among the compounds represented by the aforementioned formula (1), the compounds represented by the following formula (1-b) are preferred. 
In the formula, R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group and two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. Z represents a divalent bridging group, and A and B each represents a fluorine atom or a hydrogen atom. n1 represents an integer of 1-6 and n2 represents an integer of 3-8. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1. In the formula, Z and Yxe2x88x92 have the same meanings as defined for them in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1). R13, R14, R15 and m have the same meanings as defined in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1). A and B preferably represent a fluorine atom.
Among the compounds represented by the aforementioned formula (1), the compounds represented by the aforementioned formula (1-c) are further preferred.
In the formula (1-C), n1 represents an integer of 1-6 and n2 represents an integer of 3-8 provided that 2 (n1+n2) is 19 or less. R13, R14 and R15 each independently represent a substituted or unsubstituted alkyl group and two or more of R13, R14 and R15 may be taken together with the nitrogen atom to which R13, R14 and R15 bond to form a ring. X11 and X21 each independently represent xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 or xe2x80x94NR31xe2x80x94 where R31 represents a hydrogen atom or a substituent, and Z represents a divalent bridging group or a single bond. Yxe2x88x92 represents a counter anion, but Yxe2x88x92 may not be present when the intramolecular charge excluding Yxe2x88x92 is 0. m is 0 or 1. In the formula, Z and Yxe2x88x92 have the same meanings as those defined in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1). R13, R14, R15 and m have the same meanings as those defined in the aforementioned formula (1), respectively, and preferred scopes thereof are also the same as those explained for them in the formula (1).
n1 represents an integer of 1-6, preferably an integer of 1-3, further preferably 2 or 3, most preferably 2. n2 represents an integer of 3-8, more preferably 3-6, further preferably 4-6. As for preferred combination of n1 and n2, it is preferred that n1 should be 2 or 3, and n2 should be 4 or 6.
Specific examples of the compounds represented by the aforementioned formula (1) are mentioned below. However, the present invention is not limited by the following examples at all. The alkyl groups and perfluoroalkyl groups mentioned in the structures of the following exemplary compounds have straight chain structures unless otherwise indicated. In addition, the abbreviations of 2EH used in the structures mean 2-ethylhexyl. 
Examples of the usual synthesis method of the compounds represented by the aforementioned formulas (1), (1-a), (1-b) and (1-c) (these are also collectively referred to as xe2x80x9cthe compound of the present inventionxe2x80x9d hereinafter) are mentioned below. However, the present invention is not limited to these.
The compound of the present invention can be synthesized by using a fumaric acid derivative, maleic acid derivative, itaconic acid derivative, glutamic acid derivative, aspartic acid derivative or the like as a raw material. For example, when a fumaric acid derivative, maleic acid derivative or itaconic acid derivative is used as a raw material, the compound of the present invention can be synthesized by performing the Michael addition reaction using a nucleophilic species for a double bond of the raw material and then making the product into a cation using an alkylating agent.
[Aqueous Coating Composition]
The compound of the present invention is preferably used as surfactants in coating compositions for forming layers constituting various recording materials (in particular, silver halide photographic light-sensitive materials). Especially, it is particularly preferably used for forming a hydrophilic colloid layer as an uppermost layer of a photographic light-sensitive material, since it imparts effective antistatic ability and provides uniformity of coating. A coating composition containing the compound of the present invention as a surfactant will be explained hereafter.
The aqueous coating composition of the present invention contains the aforementioned surfactant of the present invention and a medium dissolving and/or dispersing the surfactant. In addition, depending on a purpose, other components may be suitably included.
In the aqueous coating composition of the present invention, the medium is preferably an aqueous medium. The aqueous medium includes water and a mixture of an organic solvent other than water (e.g., methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone etc.) with water. In the present invention, the medium of the aforementioned coating composition preferably contains 50 weight % or more of water.
In the aqueous coating composition of the present invention, a single kind of compound among the compounds of the present invention may be individually used or two or more kinds of the compounds may be used as a mixture. Further, the compound of the present invention may be used together with other surfactants. Surfactants that can be used together include various surfactants of anion type, cation type and nonion type. Moreover, the surfactants used together may be polymer surfactants, or may be fluorine-containing surfactants other than the surfactants of the present invention. The surfactants used together are more preferably anionic surfactants or nonionic surfactants. The surfactants that can be used together include, for example, those disclosed in JP-A-62-215272 (pages 649-706), Research Disclosure (RD) Items 17643, pages 26-27 (December, 1978), 18716, page 650 (November, 1979), 307105, pages 875-876 (November, 1989) and so forth.
As another component that may be contained in the aqueous coating composition of the present invention, a polymer compound can be mentioned as a typical example. The polymer compound may be a polymer soluble in an aqueous medium (henceforth referred to as xe2x80x9csoluble polymerxe2x80x9d) or may be dispersion of a polymer in water (so-called xe2x80x9cpolymer latexxe2x80x9d). The soluble polymer is not particularly limited, and examples thereof include, for example, gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose and so forth. Examples of the polymer latex include dispersions of homopolymers and copolymers of various vinyl monomers [e.g., acrylate derivatives, methacrylate derivatives, acrylamide derivatives, methacrylamide derivatives, styrene derivatives, conjugated-diene derivatives, N-vinyl compounds, O-vinyl compounds, vinylnitrile and others vinyl compounds (e.g., ethylene, vinylidene chloride)], and dispersions of condensation type polymers (e.g., polyesters, polyurethanes, polycarbonates, polyamides). Specific examples of polymer compounds of this type include the polymer compounds disclosed in JP-A-62-215272 (pages 707-763), Research Disclosure (RD) Items 17643, page 651 (December, 1978), 18716, page 650 (November, 1979), 307105, pages 873-874 (November, 1989) and so forth.
The aqueous coating composition of the present invention may contain various other compounds, and they may be dissolved or dispersed in the medium. For example, when it is used for forming a layer constituting a photographic light-sensitive material, there can be mentioned various couplers, ultraviolet absorbers, anti-color mixing agents, antistatic agents, scavengers, antifoggants, hardeners, dyes, fungicides and so forth. Further, as described above, the aqueous coating composition of the present invention is preferably used for forming a hydrophilic colloid layer as an uppermost layer of a photographic light-sensitive material, and in this case, the coating composition may contain other surfactants, matting agents, lubricants, colloidal silica, gelatin plasticizers and so forth, besides the hydrophilic colloid (e.g., gelatin) and the compound of the present invention.
The amount of the compound of the present invention is not particularly limited, and it can be arbitrarily determined depending on structure or use of a compound to be used, types and amounts of materials contained in the aqueous composition, composition of the medium and so forth. When the aqueous coating composition of the present invention is used as a coating solution for a hydrophilic colloid (gelatin) layer as an uppermost layer of a silver halide photographic light-sensitive material, for example, the concentration of the compound of the present invention is preferably 0.003-0.5 weight % in the coating composition, or preferably 0.03-5 weight % with respect to the gelatin solid content.
[Silver Halide Photographic Light-Sensitive Material]
The silver halide photographic light-sensitive material of the present invention is characterized in that it has one or more layers including a light-sensitive silver halide emulsion layer on a support and any of the layers contains the compound of the present invention. In a preferred embodiment of the silver halide photographic light-sensitive material of the present invention, it has a light-insensitive hydrophilic colloid layer as an outermost layer and this outermost layer contains the compound of the present invention.
The silver halide photographic light-sensitive material of the present invention can be produced by coating one or more kinds of the aqueous coating compositions of the present invention on a support. The method for coating the coating compositions is not particularly limited, and it may be any of the slide bead coating method, slide curtain coating method, extrusion curtain coating method and extrusion bead coating method. Among these, the slide bead coating method is preferred.
Hereafter, various materials used for the silver halide photographic light-sensitive material of the present invention will be explained by exemplifying a silver halide color photographic light-sensitive material.
Silver halide grains in silver halide grain emulsion that can be used for the silver halide photographic light-sensitive material of the present invention may be those having regular crystals such as cubic, octahedral or tetradecahedral crystals, those having irregular crystals such as spherical or tabular crystals or those having crystal defects such as twinned crystal faces, or those having composite forms thereof. Tabular grains are particularly preferred.
It is preferred that, in a tabular grain emulsion, grains having an aspect ratio of 3 or more provide 50% or more of the total projected area thereof. The projected area and aspect ratio of a tabular grain can be measured from a shadowed electron micrograph of it taken together with a reference latex sphere by the carbon replica method. A tabular grain usually has a hexagonal, triangular or circular shape when viewed in a direction perpendicular to the main plane thereof, and the aspect ratio is a value obtained by dividing a diameter of a circle having the same area as the projected area of the grain (diameter as circle) with the thickness of the grain. A higher ratio of hexagon as the shape of the tabular grains is more preferred, and the ratio of the lengths of adjacent sides of the hexagon is preferably 1:2 or less.
As for the effect of the present invention, a higher aspect ratio provides more preferred photographic performance. Therefore, it is more preferred that 50% or more of the total projected area of the tabular grains in the emulsion is provided by grains having an aspect ratio of 8 or more, more preferably 12 or more. However, if the aspect ratio becomes too high, the variation coefficient of the aforementioned grain size distribution increases. Accordingly, it is usually preferred that grains should have an aspect ratio of 50 or less.
The mean grain diameter of the silver halide grains is preferably 0.2-10.0 xcexcm, more preferably 0.5-5.0 xcexcm, as a diameter as circle. The diameter as circle is a diameter of a circle parallel to the main plane and having the same area as the projected area of the main plane. The project area of a grain can be obtained by measuring an area of the grain on an electron microphotograph and correcting it according to magnification of the photography. A mean diameter as sphere is preferably 0.1-5.0 xcexcm, more preferably 0.6-2.0 xcexcm. These ranges provide the most superior relationship of sensitivity/granularity ratio of the light-sensitive emulsion. In case of tabular grains, the mean thickness thereof is preferably 0.05-1.0 xcexcm. The mean diameter as circle used herein means an average of diameters as circle of 1000 or more grains arbitrarily collected from a uniform emulsion. The same shall apply to the mean thickness.
The silver halide grains may be monodispersed or polydispersed.
The tabular grains preferably have facing (111) main planes and side faces that connect the main planes. At least one twin plane is preferably interposed between the main planes. In the tabular grain emulsion used in the present invention, it is preferred that two twin planes are observed in each of the tabular grains. The spacing of the two twin planes can be made less than 0.012 xcexcm as described in U.S. Pat. No. 5,219,720. Further, the value obtained by dividing the distance between (111) main planes with the twin plane spacing can be made at least 15 as described in JP-A-5-249585. In the present invention, as for the side faces connecting the facing (111) main planes of the tabular grains in the emulsion, 75% or less of the total side faces are preferably composed of (111) faces. The expression of xe2x80x9c75% or less of the total side faces are composed of (111) facesxe2x80x9d used herein means that crystallographic faces other than the (111) faces exist at a proportion higher than 25% of the total side faces. While such other crystallographic faces can generally be understood as being (100) faces, other faces such as (110) faces and faces with a higher index may also be included. In the present invention, if 70% or less of the total side faces are composed of (111) faces, marked effect can be obtained.
Examples of solvent for the silver halide that can be used in the present invention include (a) organic thioethers described in U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628, JP-A-54-1019, JP-A-54-158917 etc., (b) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982 etc., (c) silver halide solvents having a thiocarbonyl group between an oxygen atom or a sulfur atom and a nitrogen atom, described in JP-A-53-144319, (d) imidazoles described in JP-A-54-100717, (e) ammonia, (f) thiocyanates and so forth.
Particularly preferred solvents are thiocyanates, ammonia and tetramethylthiourea. The amount of the solvent to be used varies depending on the type of the solvent, and in case of thiocyanates, the amount is preferably 1xc3x9710xe2x88x924 mol to 1xc3x9710xe2x88x922 mol per mol of the silver halide.
As for the method of changing the face index of a side face of tabular grain in emulsion, EP515894A1 etc. can be referred to. The polyalkyleneoxide compounds described in U.S. Pat. No. 5,252,453 etc. can also be used. As an effective method, it is possible to use face index modifiers described in U.S. Pat. Nos. 4,680,254, 4,680,255, 4,680,256, 4,684,607 etc. Usual photographic spectral sensitization dyes can also be used as face index modifiers similar to those mentioned above.
The silver halide emulsion can be prepared by various methods so long as it satisfies the requirements described above. In general, the preparation of a tabular grain emulsion basically includes three steps of nucleation, ripening and growth. In the nucleation step of the tabular grain emulsion used in the present invention, it is extremely effective to use gelatin with a small methionine content as described in U.S. Pat. Nos. 4,713,320 and 4,942,120, perform the nucleation at a high pBr as described in U.S. Pat. No. 4,914,014 and perform nucleation within a short time period as described in JP-A-2-222940. In the ripening step of the tabular grain emulsion, it may be effective to perform the ripening in the presence of base at a low concentration as described in U.S. Pat. No. 5,254,453 or at a high pH as described in U.S. Pat. No. 5,013,641. In the growth step of the tabular grains in the emulsion, it is particularly effective to perform the growth at a low temperature as described in U.S. Pat. No. 5,248,587 or use fine silver iodide grains as described in U.S. Pat. Nos. 4,672,027 and 4,693,964. Furthermore, it is also preferable to attain the growth by ripening with addition of silver bromide, silver iodobromide or silver chloroiodobromide fine grain emulsion. It is also possible to supply the aforementioned fine grain emulsion by using a stirring machine described in JP-A-10-43570.
The silver halide emulsion preferably contains silver iodobromide, silver iodochloride, silver bromochloride or silver iodochlorobromide. More preferably, it comprises silver iodobromide or silver iodochlorobromide. In case of silver iodochlorobromide, although the emulsion may contain silver chloride, the silver chloride content is preferably 8 mol % or less, more preferably 3 mol % or less or 0 mol %. As for the silver iodide content, since variation coefficient of the grain size distribution is preferably 25% or less, the silver iodide content is preferably 20 mol % or less. By reducing the silver iodide content, it becomes easy to make small the variation coefficient of the grain size distribution in the tabular grain emulsion. In particular, variation coefficient of grain size distribution in the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol % or less. Irrespective of the silver iodide content, the variation coefficient of silver iodide content distribution among the grains is preferably 20% or less, particularly preferably 10% or less.
The silver halide emulsion preferably has a certain structure of silver iodide distribution in the grains. In this case, the structure of the silver iodide distribution may be double, triple or quadruple structure, or a structure of further higher order.
The structure of the grains in the silver halide emulsion is also preferably, for example, a triple structure consisting of silver bromide/silver iodobromide/silver bromide or a further higher order structure. The boarders of silver iodide contents in the structures may be definite borders, or the content may be changed continuously and gradually. In general, in measurement of silver iodide content using powder X-ray diffractometry, definite two peaks of different silver iodide contents are not detected, and there is obtained an X-ray diffraction profile having a portion raised along the direction to a higher silver iodide content.
Further, it is preferred that the silver iodide content is preferably higher in an internal portion than that of a surface portion, and the silver iodide content of an internal portion is higher than that of a surface portion by, preferably 5 mol % or more, more preferably 7 mol % or more.
When the silver halide emulsion comprises tabular grains, it is preferable to use tabular grains having dislocation lines. Dislocation lines in tabular grains can be observed by a direct method described in, for example, J. F. Hamilton, Phot. Sci. Eng., 11, 57 (1967) or T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213 (1972), which is performed at a low temperature by using a transmission electron microscope. That is, silver halide grains are carefully extracted from an emulsion so as not to produce a pressure that forms dislocation lines in the grains and placed on a mesh for electron microscopic observation. The sample is observed by a transmission method while being cooled to prevent damages (e.g., print out) caused by electron rays. In this method, as the thickness of a grain increases, it becomes more difficult to transmit electron rays through it. Therefore, grains can be observed more clearly by using an electron microscope of high voltage type (200 kV or higher for a grain having a thickness of 0.25 xcexcm). A photograph of grains obtained by this method shows positions and number of dislocation lines in each grain when the grain is viewed in a direction perpendicular to the main plane.
The average number of dislocation lines is preferably 10 or more, more preferably 20 or more, per grain. If dislocation lines are densely present or cross each other when observed, it is sometimes impossible to accurately count the number of dislocation lines per grain. Even in such cases, however, dislocation lines can be roughly counted to such an extent as in a unit of ten lines, i.e., 10 lines, 20 lines, 30 lines and so on. Accordingly, these cases can be clearly distinguished from cases where only several dislocation lines are present. The average number of dislocation lines per grain is obtained as a number average by counting the dislocation lines of 100 grains or more.
The silver halide grains can be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization in any steps of production of the silver halide emulsion. It is preferable to combine two or more kinds of sensitization processes. Various types of emulsions can be prepared depending on the stage at which the grains are subjected to chemical sensitization. There are a type in which chemical sensitization nuclei are embedded in the inside of the grains, a type in which the nuclei are embedded in grains at shallow positions from the surfaces and a type in which the nuclei are prepared on the surfaces of the grains. The chemical sensitization nuclei can be formed at desired sites by controlling the conditions for the preparation of emulsion depending on the purpose. However, it is preferred that at least one kind of chemical sensitization nuclei should be formed in the vicinity of the surfaces of the grains.
Chemical sensitization that can be preferably performed is chalcogenide sensitization, noble metal sensitization or a combination thereof. These types of chemical sensitization can be conducted using active gelatin as described in T. H. James, The Theory of the Photographic Process, 4th ed., pages 67 to 76, Macmillan (1977), or sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of multiple kinds of these sensitizers can be used at pAg of 5-10 and pH of 5-8 at a temperature of 30-80xc2x0 C. as described in Research Disclosure, vol. 120, Item 12008 (April, 1974), vol. 34, Item 13452 (June, 1975), U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, 3,904,415 and British Patent 1,315,755. As for the noble metal sensitization, salts of noble metals such as gold, platinum, palladium and iridium can be used. In particular, gold sensitization, palladium sensitization or the combination of the both is preferred.
In the gold sensitization, it is possible to use known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide. For the palladium sensitization, a divalent or tetravalent salt of palladium can be used. Preferred examples of the palladium compound used for the palladium sensitization include those represented as R2PdX6 or R2PdX4 wherein R represents a hydrogen atom, an alkali metal atom or an ammonium group and X represents a halogen atom, i.e., a chlorine, bromine or iodine atom. More specifically, K2PdCl4, (NH4)2PdCl6, Na2PdCl4, (NH4)2PdCl4, Li2PdCl4, Na2PdCl6 and K2PdBr4 are preferred. The gold compound and palladium compound are preferably used in combination with a thiocyanate or selenocyanate.
As the sulfur sensitizer, there can be used hypo, thiourea compounds, rhodanine compounds and sulfur-containing compounds described in U.S. Pat. Nos. 3,857,711, 4,266,018, and 4,054,457. The chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Examples of useful chemical sensitization aid are compounds known as those capable of suppressing fog and increasing sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of the chemical sensitization aid and modifier are described in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and G. F. Duffin, xe2x80x9cChemistry of Photographic Emulsionxe2x80x9d, pages 138-143.
It is preferable to also perform gold sensitization for the silver halide emulsion. The amount of a gold sensitizer is preferably 1xc3x9710xe2x88x924 to 1xc3x9710xe2x88x927 mol, more preferably 1xc3x9710xe2x88x925 to 5xc3x9710xe2x88x927 mol, per mol of silver halide. The amount of a palladium compound is preferably 1xc3x9710xe2x88x923 to 5xc3x9710xe2x88x927 mol per mol of silver halide. The amount of a thiocyan compound or selenocyan compound is preferably 5xc3x9710xe2x88x922 to 1xc3x9710xe2x88x926 mol per mol of silver halide. The amount of a sulfur sensitizer used for the silver halide grains is preferably 1xc3x9710xe2x88x924 to 1xc3x9710xe2x88x927 mol, more preferably 1xc3x9710xe2x88x925 to 5xc3x9710xe2x88x927 mol, per mol of silver halide.
Selenium sensitization is a preferred sensitization technique for a silver halide emulsion. In the selenium sensitization, known unstable selenium compounds are used. Specifically, selenium compounds such as colloidal metallic selenium, selenoureas (e.g., N,N-dimethylselenourea, N,N-diethylselenourea etc.), selenoketones and selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, noble metal sensitization or both of them. For example, it is preferable to add a thiocyanate before addition of the aforementioned spectral sensitization dye and chemical sensitizer. More preferably, it is added after the formation of grains, further preferably it is added after completion of the desalting step. It is preferable to add a thiocyanate also at the time of the chemical sensitization, that is, it is preferable to add a thiocyanate twice or more times during the chemical sensitization. As the thiocyanate, there are used potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and so forth. The thiocyanate is usually added after being dissolved in an aqueous solution or a water-miscible solvent. The amount thereof is 1xc3x9710xe2x88x925 to 1xc3x9710xe2x88x922 mol, more preferably 5xc3x9710xe2x88x925 to 5xc3x9710xe2x88x923 mol, per mol of silver halide.
As a protective colloid used at the time of preparation of the silver halide emulsion or a binder of the other hydrophilic colloid layers, gelatin may be advantageously used. However, other hydrophilic binders may also be used. For example, there can be used derivatives of gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymetholcellulose and cellulose sulfate, sodium alginate, derivatives of saccharide such as derivatives of starch; various synthetic hydrophilic polymers including homopolymers and copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole and so forth.
As gelatin, besides lime-processed gelatin, acid-treated gelatin and enzyme-processed gelatin described in Bull. Soc. Sci. Photo. Japan. No. 16, p.30 (1966) may be used. In addition, a hydrolyzed product or an enzyme-decomposed product of gelatin can also be used.
It is preferable to wash the obtained emulsion with water for desalting and then disperse it in a newly prepared protective colloid. Although temperature of the washing with water can be selected depending on the purpose, it is preferably selected in the range of 5-50xc2x0 C. Although pH for the washing can also be selected depending on the purpose, it is preferably 2-10, more preferably 3-8. The pAg for the washing is preferably 5-10, although it can also be selected depending on the purpose. The method for washing with water can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation precipitation and ion exchange. As for the coagulation precipitation, there can be selected a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative or the like.
It is preferable to make a salt of metal ion exist during the preparation of the emulsion, for example, during grain formation, desalting or chemical sensitization or before coating depending on the purpose. The metal ion salt is preferably added during grain formation when it is doped into grains, or after grain formation and before the completion of chemical sensitization when it is used to modify the grain surface or used as a chemical sensitizer. It may be doped into an overall grain, or it is also possible to dope it into only a core, shell or epitaxial portion, or base grain. Examples of the metal ion include those of Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, Bi and so forth. These metals can be added so long as they are in the form of a salt that can be dissolved during grain formation, such as ammonium salt, acetate, nitrate, sulfate, phosphate, hydroxy acid salt, 6-coordinated complex salt or 4-coordinated complex salt. Examples thereof are CdBr2, CdCl2, Cd(NO3)2, Pb(NO3)2, Pb(CH3COO)2, K3[Fe(CN)6], (NH4)4[Fe(CN)6], K3IrCl6, (NH4)3RhCl6, K4Ru(CN)6 and so forth. The ligand of the complex compounds can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These metal compounds can be used either singly or as a combination of two or more types of them.
The metal compound is preferably added after being dissolved in water or an appropriate organic solvent such as methanol or acetone. To stabilize the solution, an aqueous hydrogen halide solution (e.g., HCl and HBr) or an alkali halide (e.g., KCl, NaCl, Kbr, NaBr) can be added. It is also possible to add acid or alkali, if necessary. The metal compound can be added to a reaction vessel either before or during grain formation. Alternatively, the metal compound can be added to an aqueous solution of a water-soluble silver salt (e.g., AgNO3) or an alkali halide (e.g., NaCl, KBr, KI), and continuously added during the formation of silver halide grains. Furthermore, a solution of the metal compound can be prepared separately from solutions of the water-soluble silver salt and alkali halide and continuously added in a proper period during the grain formation. Further, it is also possible to combine several different addition methods.
It is sometimes useful to use a method of adding a chalcogenide compound during the preparation of the emulsion as described in U.S. Pat. No. 3,772,031. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate can be present.
It is preferable to use an oxidizer for silver during the process of producing the emulsion. However, silver nuclei that contribute to enhancement of the sensitivity obtained by the reduction sensitization on the surface of the grain needs to remain to some extent. A compound that converts extremely fine silver grains, which are produced as a by-product in the processes of formation of silver halide grains and chemical sensitization, into silver ions is effective. The silver ions produced may form a silver salt hardly soluble in water such as silver halide, silver sulfide or silver selenide, or a silver salt easily dissolved in water such as silver nitrate.
Preferred oxidizers are inorganic oxidizers consisting of thiosulfonates and organic oxidizers consisting of quinones.
The photographic emulsion used in the present invention can contain various compounds in order to prevent fog or stabilize photographic performance during the production process, storage or photographic process of the light-sensitive material. That is, various compounds known as an antifoggant or a stabilizer can be added, and examples thereof include, for example, thiazoles such as benzothiazolium salt, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadolinethione; azaindenes such as triazaindenes, tetrazaindenes (in particular, hydroxy-substituted (1,3,3a,7)-tetrazaindenes) and pentazaindenes. For example, the compounds described in U.S. Pat. Nos. 3,954,474 and 3,982,947 and Japanese Patent Publication (Kokoku, hereinafter referred to as JP-B) No. 52-28660 can be used. One class of preferred compounds are those described in JP-B-7-78597 (Japanese Patent Application No. 62-47225). The antifoggant and the stabilizer can be added at any of different times, for example, they can be added before, during and after the grain formation, during the washing with water, during dispersion after the washing, before, during and after the chemical sensitization and before coating, depending on the purpose. The antifoggant and the stabilizer can be added during preparation of the emulsion to achieve their original fog preventing effect and stabilizing effect, and in addition, they can be used for various purposes of, for example, controlling crystal habit of grains, decreasing grain size, decreasing solubility of grains, controlling chemical sensitization, controlling arrangement of dyes and so forth.
Techniques such as those for layer arrangement, silver halide emulsions, dye forming couplers, functional couplers such as DIR couplers, various additives and development usable for the emulsion and the photographic light-sensitive material using the emulsion are described in European Patent No. 0565096A1 (published on Oct. 13, 1993) and the patents cited in it. The individual items and the corresponding portions are listed below.
1. Layer structure: page 61, lines 23-35, page 61, line 41 to page 62, line 14
2. Intermediate layer: page 61, lines 36-40
3. Interlayer effect imparting layer: page 62, lines 15-18
4. Silver halide halogen composition: page 62, lines 21-25
5. Silver halide grain crystal habit: page 62, lines 26-30
6. Silver halide grain size: page 62, lines 31-34
7. Emulsion preparation method: page 62, lines 35-40
8. Silver halide grain size distribution: page 62, lines 41-42
9. Tabular grains: page 62, lines 43-46
10. Internal structures of grain: page 62, lines 47-53
11. Latent image formation type of emulsion: page 62, line 54 to page 63, line 5
12. Physical ripening and chemical ripening of emulsion: page 63, lines 6-9
13. Use of emulsion mixture: page 63, lines 10-13
14. Fogged emulsion: page 63, lines 14-31
15. Light-insensitive emulsion: page 63, lines 32-43
16. Silver coating amount: page 63, lines 49-50
17. Photographic additives: described in Research Disclosure (RD) Item 17643 (December, 1978), Item 18716 (November, 1979), and Item 307105 (November, 1989). The individual items and the corresponding portions of descriptions are mentioned below.
18. Formaldehyde scavenger: page 64, lines 54-57
19. Mercapto type antifoggant: page 65, lines 1-2
20. Agents releasing fogging agent etc.: page 65, lines 3-7
21. Dyes: page 65, lines 7-10
22. General review for color couplers: page 65, lines 11-13
23. Yellow, magenta and cyan couplers: page 65, lines 14-25
24. Polymer coupler: page 65, lines 26-28
25. Diffusing dye forming coupler: page 65, lines 29-31
26. Colored coupler: page 65, lines 32-38
27. General review for functional couplers: page 65, lines 39-44
28. Bleaching accelerator releasing coupler: page 65, lines 45-48
29. Development accelerator releasing coupler: page 65, lines 49-53
30. Other DIR couplers: page 65, line 54 to page 66, line 4
31. Coupler diffusing method: page 66, lines 5-28
32. Antiseptic and mildewproofing agents: page 66, lines 29-33
33. Types of light-sensitive materials: page 66, lines 34-36
34. Film thickness and swelling speed of light-sensitive layer: page 66, line 40 to page 67, line 1
35. Back layer: page 67, lines 3-8
36. General review for development treatment: page 67, lines 9-11
37. Developer and developing agent: page 67, lines 12-30
38. Developer additives: page 67, lines 31-44
39. Reversal processing: page 67, lines 45-56
40. Processing solution aperture ratio: page 67, line 57 to page 68, line 12
41. Development time page 68, lines 13-15
42. Bleach fixing, bleaching and fixing: page 68, line 16 to page 69, line 31
43. Automatic processor: page 69, lines 32-40
44. Washing, rinsing and stabilization: page 69, line 41 to page 70, line 18
45. Replenishment and reuse of processing solutions: page 70, lines 19-23
46. Incorporation of developing agent into light-sensitive material: page 70, lines 24-33
47. Development temperature: page 70, lines 34-38
48. Application to film with lens: page 70, lines 39-41
The bleaching solution described in European Patent No. 602600, which contains 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, ferric salt such as ferric nitrate and persulfate, can also be preferably used. When this bleaching solution is used, it is preferable to interpose a stop step and a step of washing with water between the color development step and the bleaching step and use an organic acid such as acetic acid, succinic acid or maleic acid for a stop solution. Furthermore, for the purposes of pH adjustment and bleaching fog, the bleaching solution preferably contains 0.1-2 mol/L of an organic acid such as acetic acid, succinic acid, maleic acid, glutaric acid or adipic acid.